<title lang="zh">由乙醇原料製造乙烯的方法</title><technical-field><p>本發明是有關於一種由乙醇原料製造乙烯的方法，特別是指一種使用承載型雜多酸鹽催化劑進行乙醇脫水反應以製造乙烯的方法。</p></technical-field><background-art><p>乙烯為塑料的主要成分，其製備方式可透過裂解石油烴類形成乙烯，或者使乙醇進行脫水反應形成乙烯。隨著石油資源減少，使用石油製造乙烯的成本日趨昂貴，然而，相較於石油，乙醇製造乙烯的製程中可以使用透過葡萄糖、澱粉等經發酵所製得的生質乙醇，且相較於裂解石油烴類形成乙烯，使用生質乙醇進行脫水反應來製造生質乙烯可以大幅減少溫室氣體排放量，因此現在從乙醇製造乙烯是業界的主流技術。</p><p>乙醇的脫水反應包含以下兩種反應路徑：其中之一是，乙醇脫水直接形成乙烯及水，另一是乙醇脫水先形成中間產物乙醚，乙醚後續可再形成乙烯。乙醇的脫水反應是吸熱反應且為可逆反應，反應溫度越高越有利於乙醇脫水反應的進行。</p><p>目前乙醇製造乙烯的商業化生產方式，例如採用Scientific Design公司或Petron公司的技術，是使用以γ-Al
<sub>2</sub>O
<sub>3</sub>為基質的催化劑，乙醇進行脫水反應所需的溫度高達350至450℃。但由於乙醇脫水反應的操作溫度相當地高，不僅增加能耗，也增加製程成本。
</p><p>有鑒於乙醇脫水反應有反應溫度過高的問題，目前的研究方向是希望能夠降低乙醇脫水反應的溫度。例如，英國石油公司的美國專利US 8426664中揭露一種由乙醇原料製造乙烯的方法，是將乙醇原料在氣相脫水反應器中反應，使乙醇在160至270℃的溫度及在高於0.1MPa但低於4.5MPa的壓力下被轉化成含有乙烯、二乙醚、水及未轉化乙醇的產物流，其中，乙醇脫水反應中可使用例如將雜多酸溶液含浸到氧化矽載體所製得的多相催化劑。該美國專利揭露其方法會有15至85%的乙醚在製程中循環，表示其單次反應得到的產物中大部分為乙醚，乙烯的比例並不高。</p></background-art><disclosure><p>因此，本發明之目的，即在提供一種由乙醇原料製造乙烯的方法。</p><p>於是，本發明由乙醇原料製造乙烯的方法，包含以下步驟： 在一承載型雜多酸鹽催化劑的存在下，使一乙醇原料進行一脫水反應，其中，該承載型雜多酸鹽催化劑包含一雜多酸鹽化合物及一承載該雜多酸鹽化合物的載體，該雜多酸鹽化合物是選自於由化學式1、化學式2及化學式3所組成的群組，
<img he="21" wi="160" img-format="jpg" id="i0002" img-content="drawing" orientation="portrait" inline="no" file="TWI645899B_D0001.tif" />化學式1
<img he="25" wi="160" img-format="jpg" id="i0002" img-content="drawing" orientation="portrait" inline="no" file="TWI645899B_D0002.tif" />化學式2
<img he="25" wi="159" img-format="jpg" id="i0002" img-content="drawing" orientation="portrait" inline="no" file="TWI645899B_D0003.tif" />化學式3 化學式1至3中，M
<sup>a</sup>、M
<sup>b</sup>、M
<sup>c</sup>各自獨立地選自於由銅、銀、金、鋅、鎘及汞所組成的群組， X
<sup>a</sup>是選自於由矽及鍺所組成的群組， X
<sup>b</sup>及X
<sup>c</sup>各自獨立地選自於由磷及砷所組成的群組， M
<sup>d</sup>、M
<sup>e</sup>及M
<sup>f</sup>各自獨立地選自於由鉬及鎢所組成的群組， n表示1至4的正整數，q表示1至3的正整數，p表示1至6的正整數。
</p><p>本發明之功效在於：該由乙醇原料製造乙烯的方法透過使用該承載型雜多酸鹽催化劑，能夠有效降低乙醇進行脫水反應時的反應溫度，從而降低能耗，且該由乙醇原料製造乙烯的方法能得到較高的乙醇轉化率及較高的乙烯選擇率。</p><p>本發明之另一功效在於：該由乙醇原料製造乙烯的方法中，即使將已用於催化乙醇脫水反應的該承載型雜多酸鹽催化劑回收再重複使用，該由乙醇原料製造乙烯的方法仍能在較低的反應溫度進行乙醇脫水反應，並得到高的乙醇轉化率及乙烯選擇率。</p></disclosure><mode-for-invention><p>以下就本發明內容進行詳細說明：</p><p>該由乙醇原料製造乙烯的方法的具體操作方式包含以下步驟：將該承載型雜多酸鹽催化劑置於一反應器中；使該乙醇原料汽化成乙醇氣體；以及，以一載流氣體將該乙醇氣體帶入該反應器中，並在該承載型雜多酸鹽催化劑的存在下使該乙醇氣體進行乙醇的脫水反應，得到一包含乙烯的氣體產物。因該脫水反應生成的氣體產物中除了含有乙烯，還會含有乙醚及水，更佳地，該由乙醇原料製造乙烯的方法還可視需要包含以下步驟：使該氣體產物中的乙醚及水冷卻，以分離出乙烯。其中，使該氣體產物中的乙醚及水冷卻的方式例如但不限於使用氣液分離器。所得到的乙醚可進一步回收至該反應器中再進行脫水反應形成乙烯，能更進一步提升乙烯的產率。</p><p>其中，該乙醇原料泛指含有乙醇的原料，其濃度無特別限制，該乙醇原料的濃度範圍例如為5至95 %(v/v)。</p><p>該載流氣體例如但不限於氮氣、空氣。該載流氣體的溼度無特別限制，例如但不限於1至20 %。</p><p>該脫水反應時的反應參數無特別限制，空速範圍例如但不限於0.5至10 h
<sup>-1</sup>，壓力範圍例如但不限於0.1至2 MPa。
</p><p>較佳地，該脫水反應的溫度範圍為180至450℃；更佳地，該脫水反應的溫度範圍為180至300℃；最佳地，該脫水反應的溫度範圍為180至250℃。要特別說明的是，該由乙醇原料製造乙烯的方法中，該脫水反應的溫度範圍為180至250℃時即能達到相當高的乙醇轉化率及高的乙烯選擇率，但該由乙醇原料製造乙烯的方法中該脫水反應的溫度範圍不應受限為180至250℃，也可為180至300℃，或者180至450℃，且可預期地，當脫水反應的溫度越高時，乙醇轉化率及乙烯選擇率也會相對地再提高。</p><p>該承載型雜多酸鹽催化劑包含該雜多酸鹽化合物及該載體。</p><p>該雜多酸鹽化合物是選自於由化學式1、化學式2及化學式3所組成的群組。
<img he="21" wi="160" img-format="jpg" id="i0008" img-content="drawing" orientation="portrait" inline="no" file="TWI645899B_D0001.tif" />化學式1
<img he="25" wi="160" img-format="jpg" id="i0008" img-content="drawing" orientation="portrait" inline="no" file="TWI645899B_D0002.tif" />化學式2
<img he="25" wi="159" img-format="jpg" id="i0008" img-content="drawing" orientation="portrait" inline="no" file="TWI645899B_D0003.tif" />化學式3 化學式1至3中，M
<sup>a</sup>、M
<sup>b</sup>、M
<sup>c</sup>各自獨立地選自於由銅、銀、金、鋅、鎘及汞所組成的群組， X
<sup>a</sup>是選自於由矽及鍺所組成的群組， X
<sup>b</sup>及X
<sup>c</sup>各自獨立地選自於由磷及砷所組成的群組， M
<sup>d</sup>、M
<sup>e</sup>及M
<sup>f</sup>各自獨立地選自於由鉬及鎢所組成的群組， n表示1至4的正整數，q表示1至3的正整數，p表示1至6的正整數。
</p><p>較佳地，該化學式1至3中，M
<sup>a</sup>、M
<sup>b</sup>及M
<sup>c</sup>各自獨立地選自於由銅、銀、金及鋅所組成的群組。更佳地，該化學式1至3中，M
<sup>a</sup>、M
<sup>b</sup>及M
<sup>c</sup>各自獨立地選自於由銅及銀所組成的群組。
</p><p>較佳地，該化學式1中，X
<sup>a</sup>是選自於矽，M
<sup>d</sup>是選自於鎢。
</p><p>較佳地，該化學式2及3中，X
<sup>b</sup>及X
<sup>c</sup>各自獨立地選自於磷，M
<sup>e</sup>及M
<sup>f</sup>各自獨立地選自於鎢。
</p><p>該化學式1的具體例例如但不限於 (AgH
<sub>3</sub>)SiW
<sub>12</sub>O
<sub>40</sub>、 (CuH
<sub>3</sub>)SiW
<sub>12</sub>O
<sub>40</sub>等。
</p><p>該化學式2的具體例例如但不限於(AgH
<sub>2</sub>)P W
<sub>12</sub>O
<sub>40</sub>、(CuH
<sub>2</sub>)PW
<sub>12</sub>O
<sub>40</sub>等。
</p><p>該化學式3的具體例例如但不限於 (AgH
<sub>5</sub>)P
<sub>2</sub>W
<sub>18</sub>O
<sub>62</sub>、 (CuH
<sub>5</sub>)P
<sub>2</sub>W
<sub>18</sub>O
<sub>62</sub>等。
</p><p>較佳地，該承載型雜多酸鹽催化劑的載體是選自於由二氧化矽(silica)、蒙脱石(montmorillonite)、未改質黏土(clay)、膨潤土(bentonite)、矽藻土(celite)、二氧化鈦、活性碳(activated carbon)、氧化鋁、二氧化矽-氧化鋁共溶膠(silica-alumina cogel)、二氧化矽-二氧化鈦共溶膠(silica-titania cogel)、二氧化矽-氧化鋯共溶膠(silica-zirconia cogel)、碳塗覆的氧化鋁(carbon coated alumina)、沸石(zeolite)、氧化鋅及火焰熱解氧化物(flame pyrolysed oxide)所組成的群組。</p><p>較佳地，化學式1至3中，以該承載型雜多酸鹽催化劑的總量為100 wt%，該M
<sup>a</sup>、M
<sup>b</sup>及M
<sup>c</sup>的含量範圍各自獨立地為0.5 wt%以上。更佳地，化學式1至3中，以該承載型雜多酸鹽催化劑的總量為100 wt%，該M
<sup>a</sup>、M
<sup>b</sup>及M
<sup>c</sup>的含量範圍各自獨立地為0.5至10wt%。最佳地，化學式1至3中，以該承載型雜多酸鹽催化劑的總量為100 wt%，該M
<sup>a</sup>、M
<sup>b</sup>及M
<sup>c</sup>的含量範圍各自獨立地為1至6wt%。
</p><p>該承載型雜多酸鹽催化劑的製備方式包含以下步驟：(1).提供一承載型雜多酸催化劑，其中，該承載型雜多酸催化劑含有一雜多酸以及一承載該雜多酸的載體；(2).提供一金屬鹽溶液，其中金屬的種類是選自於由銅、銀、金、鋅、鎘及汞所組成的群組；以及(3).使該承載型雜多酸催化劑與該金屬鹽溶液反應得到一粗產物，乾燥粗產物後即得到該承載型雜多酸鹽催化劑。</p><p>較佳地，該承載型雜多酸催化劑的製備方式例如但不限於初濕含浸法(incipient wetness impregnation)，其具體步驟詳述如下：(1).將一雜多酸溶解於水中，得到一雜多酸溶液；及(2).將該雜多酸溶液與一載體混合得到一混合物，乾燥該混合物後即得到該承載型雜多酸催化劑。</p><p>較佳地，該雜多酸是選自於由具有Keggin結構的雜多酸、及具有Dawson結構的雜多酸所組成的群組。更佳地，該雜多酸是選自於由化學式4、化學式5及化學式6所組成的群組，
<img he="21" wi="103" img-format="jpg" id="i0019" img-content="drawing" orientation="portrait" inline="no" file="TWI645899B_D0007.tif" />化學式4
<img he="21" wi="103" img-format="jpg" id="i0019" img-content="drawing" orientation="portrait" inline="no" file="TWI645899B_D0008.tif" />化學式5
<img he="21" wi="107" img-format="jpg" id="i0019" img-content="drawing" orientation="portrait" inline="no" file="TWI645899B_D0009.tif" />化學式6 化學式4至6中，X
<sup>a</sup>是選自於由矽及鍺所組成的群組，X
<sup>b</sup>及X
<sup>c</sup>各自獨立地選自於由磷及砷所組成的群組，M
<sup>d</sup>、M
<sup>e</sup>及M
<sup>f</sup>各自獨立地選自於由鉬及鎢所組成的群組。 較佳地，該雜多酸是選自於磷鎢酸(phosphotungstic acid)、磷鉬酸(phosphomomlybdic acid)、矽鎢酸(silicotungstic acid)及矽鉬酸(silicomolybdic acid)所組成的群組。更佳地，該雜多酸是選自於磷鎢酸及矽鎢酸所組成的群組。
</p><p>該雜多酸溶液的濃度範圍例如但不限於5至50wt%。</p><p>該載體的種類是如上所述，於此不再贅述。</p><p>該雜多酸溶液與該載體的重量比例範圍例如但不限於0.5：1至1：5。</p><p>乾燥該雜多酸溶液與該載體的混合物的方式例如但不限於以80至150℃的溫度範圍加熱該混合物。</p><p>該金屬鹽溶液是將一金屬鹽溶解於水中所製得。該金屬鹽的具體例為硝酸銅、硝酸銀、氯金酸鹽、硝酸鋅、硝酸鎘、硝酸汞等。該金屬鹽溶液的濃度範圍為1至50wt%。</p><p>該承載型雜多酸催化劑與該金屬鹽溶液的重量比例範圍例如但不限於100：0.5至100：10。</p><p>該承載型雜多酸催化劑及該金屬鹽溶液進行反應形成的粗產物的乾燥方式例如但不限於以80至150℃溫度範圍加熱該粗產物。</p><p>本發明將就以下實施例來作進一步說明，但應瞭解的是，該實施例僅為例示說明之用，而不應被解釋為本發明實施之限制。</p><p>〔實施例〕</p><p>首先說明在以下各實施例中使用的承載型矽鎢酸催化劑及承載型磷鎢酸催化劑：</p><p>1.承載型矽鎢酸催化劑的製備方式：將6 g的矽鎢酸溶解於12 ml的水中，得到一矽鎢酸溶液。將18 g的該矽鎢酸溶液與6 g的二氧化矽(廠商型號： UniRegion Bio-Tech)混合，以130℃乾燥後即得到該承載型矽鎢酸催化劑。</p><p>2. 承載型磷鎢酸催化劑的製備方式：將6 g的磷鎢酸溶解於12 ml的水中，得到一磷鎢酸溶液。將18 g的該磷鎢酸溶液與6 g的二氧化矽(廠商型號： UniRegion Bio-Tech)混合，乾燥後即得到該承載型磷鎢酸催化劑。</p><p>[實施例1]</p><p>將0.189 g的硝酸銀溶解於3 ml的蒸餾水，得到一硝酸銀溶液。將該硝酸銀溶液慢慢滴入總重為12 g的承載型矽鎢酸催化劑中並攪拌均勻，得到一粗產物。將該粗產物置於烘箱中以130℃乾燥後，得到一承載型矽鎢酸銀鹽催化劑[矽鎢酸銀鹽化合物為(AgH
<sub>3</sub>)SiW
<sub>12</sub>O
<sub>40</sub>，銀的含量為1 wt%]。將3 ml的該承載型矽鎢酸銀鹽催化劑置於一固定床反應器中。利用一液體控制幫浦(liquid control pump)將95%(v/v)的乙醇泵入一預熱槽中汽化成乙醇氣體，並以氮氣作為載流氣體(濕度為5%)將乙醇氣體帶入該固定床反應器中，在空速為1 h
<sup>-1</sup>、反應溫度為220℃，以及反應壓力為0.1 MPa的條件下進行乙醇的脫水反應，得到實施例1的氣體產物。
</p><p>[實施例2]</p><p>將0.992 g的硝酸銀溶解於3 ml的蒸餾水，得到一硝酸銀溶液。將該硝酸銀溶液慢慢滴入總重為12 g的承載型矽鎢酸催化劑中並攪拌均勻，得到一粗產物。將該粗產物置於烘箱中以130℃乾燥後，得到一承載型矽鎢酸銀鹽催化劑[矽鎢酸銀鹽化合物為(AgH
<sub>3</sub>)SiW
<sub>12</sub>O
<sub>40</sub>，銀的含量為5 wt%]。將3 ml的該承載型矽鎢酸銀鹽催化劑置於一固定床反應器中。利用一液體質量控制幫浦將95%(v/v)的乙醇泵入一預熱槽中汽化成乙醇氣體，並以氮氣作為載流氣體(濕度為5%)將乙醇氣體帶入該固定床反應器中，在空速為1 h
<sup>-1</sup>、反應溫度為200℃，以及反應壓力為0.1 MPa的條件下進行乙醇的脫水反應，得到實施例2的氣體產物。
</p><p>[實施例3]</p><p>以與實施例2相同的步驟進行實施例3，差別在於乙醇的脫水反應是在反應溫度為220℃的條件下進行，得到實施例3的氣體產物。</p><p>[實施例4]</p><p>以與實施例2相同的步驟進行實施例4，差別在於乙醇的脫水反應是在反應溫度為250℃的條件下進行，得到實施例4的氣體產物。</p><p>[實施例5]</p><p>將0.901 g的硝酸銅溶解於3 ml的蒸餾水，得到一硝酸銅溶液。將該硝酸銅溶液慢慢滴入總重為12 g的承載型矽鎢酸催化劑中並攪拌均勻，得到一粗產物。將該粗產物置於烘箱中以130℃乾燥後，得到一承載型矽鎢酸銅鹽催化劑[矽鎢酸銅鹽化合物為(CuH
<sub>3</sub>)SiW
<sub>12</sub>O
<sub>40</sub>，銅的含量為2.5 wt%]。將3 ml的該承載型矽鎢酸銅鹽催化劑置於一固定床反應器中。利用一液體質量控制幫浦將95%(v/v)的乙醇泵入一預熱槽中汽化成乙醇氣體，並以氮氣作為載流氣體(濕度為5%)將乙醇氣體帶入該固定床反應器中，在空速為1 h
<sup>-1</sup>、反應溫度為220℃，以及反應壓力為0.1MPa的條件下進行乙醇的脫水反應，得到實施例5的氣體產物。
</p><p>[實施例6]</p><p>將0.992 g的硝酸銀溶解於3 ml的蒸餾水，得到一硝酸銀溶液。將該硝酸銀溶液慢慢滴入總重為12 g的承載型磷鎢酸催化劑中並攪拌均勻，得到一粗產物。將該粗產物置於烘箱中以130℃乾燥後，得到一承載型磷鎢酸銀鹽催化劑[磷鎢酸銀鹽化合物為(AgH
<sub>2</sub>)PW
<sub>12</sub>O
<sub>40</sub>，銀的含量為5 wt%]。將3 ml的該承載型磷鎢酸銀鹽催化劑置於一固定床反應器中。利用一液體質量控制幫浦將95%(v/v)的乙醇泵入一預熱槽中汽化成乙醇氣體，並以氮氣作為載流氣體(濕度為5%)將乙醇氣體帶入該固定床反應器中，在空速為1 h
<sup>-1</sup>、反應溫度為220℃，以及反應壓力為0.1 MPa的條件下進行乙醇的脫水反應，得到實施例6的氣體產物。
</p><p>[實施例7]</p><p>以與實施例3相同的步驟進行實施例7，差別在於重複使用承載型矽鎢酸銀鹽催化劑進行五次乙醇的脫水反應。</p><p>〔比較例〕</p><p>[比較例1]</p><p>將6 g的矽鎢酸溶解在12 ml的蒸餾水中，得到一矽鎢酸溶液。將該矽鎢酸溶液慢慢滴入6 g的二氧化矽中並攪拌均勻，得到一粗產物。將該粗產物置於烘箱中以130℃乾燥後，得到一多相催化劑。將3 ml的該多相催化劑置於一固定床反應器中。利用一液體質量控制幫浦將95%(v/v)的乙醇泵入一預熱槽中汽化成乙醇氣體，並以氮氣作為載流氣體(濕度為5%)將乙醇氣體帶入該固定床反應器中，在空速為1 h
<sup>-1</sup>、反應溫度為220℃，以及反應壓力為0.1 MPa的條件下進行乙醇的脫水反應，得到比較例1的氣體產物。
</p><p>[比較例2]</p><p>以與比較例1相同的步驟進行比較例2，差別在於乙醇的脫水反應是在反應溫度為250℃的條件下進行，得到比較例2的氣體產物。</p><p>[比較例3]</p><p>將6 g的磷鎢酸溶解在12 ml的蒸餾水中，得到一磷鎢酸溶液。將該磷鎢酸溶液慢慢滴入6 g的二氧化矽中並攪拌均勻，得到一粗產物。將該粗產物置於烘箱中以130℃乾燥後，得到一多相催化劑。將3 ml的該多相催化劑置於一固定床反應器中。利用一液體質量控制幫浦將95%(v/v)的乙醇泵入一預熱槽中汽化成乙醇氣體，並以氮氣作為載流氣體(濕度為5%)將乙醇氣體帶入該固定床反應器中，在空速為1 h
<sup>-1</sup>、反應溫度為220℃，以及反應壓力為0.1 MPa的條件下進行乙醇的脫水反應，得到比較例3的氣體產物。
</p><p>〔性質評價〕</p><p>使用氣相層析儀(廠商型號：Bruker 450-GC)分析每一實施例及比較例的氣體產物，以量測乙醇轉換率、乙烯選擇率及乙醚選擇率。結果如表1至表3所示。</p><p><p>表1
<tables><table><TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> 承載型雜多酸鹽催化劑 </td><td> 反應溫度(℃) </td><td> 乙醇轉化率(%) </td><td> 乙烯選擇率(%) </td><td> 乙醚選擇率(%) </td></tr><tr><td> 實施例 </td><td> 1 </td><td> 矽鎢酸銀 (銀含量1wt% ) </td><td> 220 </td><td> 99.5 </td><td> 85.2 </td><td> 11.6 </td></tr><tr><td> 2 </td><td> 矽鎢酸銀 (銀含量5wt%) </td><td> 200 </td><td> 99.4 </td><td> 94.1 </td><td> 2.4 </td></tr><tr><td> 3 </td><td> 矽鎢酸銀 (銀含量5wt%) </td><td> 220 </td><td> 99.8 </td><td> 99.5 </td><td> ＜0.5 </td></tr><tr><td> 4 </td><td> 矽鎢酸銀 (銀含量5wt%) </td><td> 250 </td><td> 99.9 </td><td> 99.6 </td><td> ＜0.5 </td></tr><tr><td> 5 </td><td> 矽鎢酸銅 (銅含量2.5wt%) </td><td> 220 </td><td> 96.1 </td><td> 86.5 </td><td> 10.7 </td></tr><tr><td> 6 </td><td> 磷鎢酸銀 (銀含量5wt%) </td><td> 220 </td><td> 98.3 </td><td> 96.8 </td><td> 1.9 </td></tr></TBODY></TABLE></table></tables></p><p>表2
<tables><table><TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> 承載型雜多酸鹽催化劑 </td><td> 反應溫度(℃) </td><td> 次數 </td><td> 乙醇轉化率(%) </td><td> 乙烯選擇率(%) </td></tr><tr><td> 實施例 </td><td> 7 </td><td> 矽鎢酸銀 (銀含量5wt%) </td><td> 220 </td><td> 第1次 </td><td> 99.8 </td><td> 99.5 </td></tr><tr><td> 第2次 </td><td> 99.8 </td><td> 99.2 </td></tr><tr><td> 第3次 </td><td> 99.7 </td><td> 99.3 </td></tr><tr><td> 第4次 </td><td> 99.9 </td><td> 99.6 </td></tr><tr><td> 第5次 </td><td> 99.8 </td><td> 99.5 </td></tr></TBODY></TABLE></table></tables></p><p>表3
<tables><table><TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> 多相催化劑 </td><td> 反應溫度(℃) </td><td> 乙醇轉化率(%) </td><td> 乙烯選擇率(%) </td><td> 乙醚選擇率(%) </td></tr><tr><td> 比較例 </td><td> 1 </td><td> 矽鎢酸 </td><td> 220 </td><td> 94.3 </td><td> 79.5 </td><td> 0.3 </td></tr><tr><td> 2 </td><td> 矽鎢酸 </td><td> 250 </td><td> 94.2 </td><td> 83.7 </td><td> 5.6 </td></tr><tr><td> 3 </td><td> 磷鎢酸 </td><td> 220 </td><td> 98.0 </td><td> 91.2 </td><td> ＜0.5 </td></tr></TBODY></TABLE></table></tables></p><p>由表1的結果可知，實施例1至6透過使用該承載型雜多酸鹽催化劑並於200至250℃的反應溫度進行乙醇的脫水反應，乙醇轉化率可達到96.1至99.9%，乙烯選擇率為85.2至99.6%。證明實施例1至6透過使用該承載型雜多酸鹽催化劑，能使乙醇脫水反應在低的反應溫度進行，且得到較高的乙醇轉化率以及較高的乙烯選擇率。實施例1至6中乙醚選擇率為小於0.5至11.6，將所得到的乙醚回收至製程中再進行脫水反應得到乙烯，有助於提升乙烯的總體產率。</p><p>更值得一提的是，由表2中實施例7的數據可知，即使將承載型磷鎢酸銀鹽催化劑重複使用五次進行乙醇脫水反應，在220℃的反應溫度仍能維持乙醇轉化率在99.7至99.9%，乙烯選擇率在99.2至99.6%。由此可知，由乙醇原料製造乙烯的方法透過使用承載型雜多酸鹽催化劑，該承載型雜多酸鹽催化劑能夠重複使用，且乙醇脫水反應仍能在低的反應溫度獲得較高的乙醇轉化率及乙烯選擇率。</p><p>由表3的結果可知，比較例1至2使用多相催化劑並於220至250℃的反應溫度進行乙醇的脫水反應，乙醇轉化率僅達到94.2至94.3%，乙烯選擇率僅為79.5至83.7%。由此可知，比較例1至2在低的反應溫度進行乙醇脫水反應時得到的乙醇轉化率及乙烯選擇率較差，若要得到較高的乙醇轉化率及乙烯選擇率，勢必要再提高乙醇脫水反應時的反應溫度。</p><p>在220℃的反應溫度下，相較於實施例6使用承載型磷鎢酸銀催化劑進行乙醇脫水反應得到的乙烯選擇率為96.8%，比較例3使用多相催化劑進行乙醇脫水反應得到的乙烯選擇率較低，僅為91.2%。由此可知，比較例3若要得到較高的乙烯選擇率，勢必要再提高乙醇脫水反應時的反應溫度。</p><p>綜上所述，本發明由乙醇原料製造乙烯的方法透過使用該承載型雜多酸鹽催化劑，能夠有效降低乙醇進行脫水反應時的反應溫度，從而降低能耗，且該由乙醇原料製造乙烯的方法在低的反應溫度進行乙醇脫水反應，能得到較高的乙醇轉化率及較高的乙烯選擇率。且該由乙醇原料製造乙烯的方法中，即使將已用於催化乙醇脫水反應的該承載型雜多酸鹽催化劑回收再重複使用，該由乙醇原料製造乙烯的方法仍能在較低的反應溫度進行乙醇脫水反應，並得到高的乙醇轉化率及乙烯選擇率，故確實能達成本發明之目的。</p><p>惟以上所述者，僅為本發明之實施例而已，當不能以此限定本發明實施之範圍，凡是依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。</p></mode-for-invention><description-of-drawings><description-of-element /></description-of-drawings><bio-deposit /><sequence-list-text /><title lang="zh">Method for producing ethylene from ethanol raw materials</title><technical-field><p>The present invention relates to a method for producing ethylene from an ethanol raw material, in particular to a carrier-type heteropoly A method in which an acid salt catalyst is subjected to an ethanol dehydration reaction to produce ethylene. </p></technical-field><background-art><p>Ethylene is the main component of plastics, which can be prepared by cracking petroleum hydrocarbons to form ethylene or dehydrating ethanol to form ethylene. With the reduction of petroleum resources, the cost of using petroleum to produce ethylene is becoming more and more expensive. However, compared with petroleum, the process of producing ethylene from ethanol can use raw ethanol produced by fermentation such as glucose and starch, and is compared with pyrolysis. The formation of ethylene from petroleum hydrocarbons and the dehydration of raw ethanol to produce bio-ethylene can significantly reduce greenhouse gas emissions. Therefore, the production of ethylene from ethanol is now the mainstream technology in the industry. </p><p>The dehydration reaction of ethanol comprises the following two reaction pathways: one of which is that ethanol dehydration directly forms ethylene and water, and the other is that ethanol is dehydrated to form an intermediate diethyl ether, and diethyl ether can be further formed into ethylene. The dehydration reaction of ethanol is an endothermic reaction and is a reversible reaction. The higher the reaction temperature, the more favorable the dehydration reaction of ethanol. </p><p>The current commercial production of ethylene from ethanol, such as the use of the technology of Scientific Design or Petron, is to use γ-Al
<sub>2</sub>O
<sub>3</sub> is a catalyst for the substrate, and the temperature required for dehydration of ethanol is as high as 350 to 450 °C. However, because the operating temperature of the ethanol dehydration reaction is quite high, not only the energy consumption is increased, but also the process cost is increased.
</p><p>In view of the problem of excessive reaction temperature in the ethanol dehydration reaction, the current research direction is to reduce the temperature of the ethanol dehydration reaction. For example, U.S. Patent No. 8,426,664 to the British Petroleum Corporation discloses a process for the production of ethylene from an ethanol feedstock by reacting an ethanol feedstock in a gas phase dehydration reactor at a temperature of from 160 to 270 ° C and above 0.1 MPa. It is converted into a product stream containing ethylene, diethyl ether, water and unconverted ethanol under a pressure of less than 4.5 MPa, wherein a polyphase obtained by impregnating a heteropoly acid solution into a cerium oxide carrier can be used, for example, in the ethanol dehydration reaction. catalyst. The U.S. patent discloses that the process will have 15 to 85% of the ether circulating in the process, indicating that most of the product obtained by the single reaction is diethyl ether, and the proportion of ethylene is not high. </p></background-art><disclosure><p> Accordingly, it is an object of the present invention to provide a process for producing ethylene from an ethanol feedstock. </p><p>Therefore, the method for producing ethylene from an ethanol raw material comprises the steps of: performing a dehydration reaction of an ethanol raw material in the presence of a supported heteropolyacid salt catalyst, wherein the supported type The heteropolyacid salt catalyst comprises a heteropolyacid salt compound and a carrier carrying the heteropolyacid salt compound selected from the group consisting of Chemical Formula 1, Chemical Formula 2 and Chemical Formula 3.
<img he="21" wi="160" img-format="jpg" id="i0002" img-content="drawing" orientation="portrait" inline="no" file="TWI645899B_D0001.tif" /> Chemical formula 1
<img he="25" wi="160" img-format="jpg" id="i0002" img-content="drawing" orientation="portrait" inline="no" file="TWI645899B_D0002.tif" /> Chemical formula 2
<img he="25" wi="159" img-format="jpg" id="i0002" img-content="drawing" orientation="portrait" inline="no" file="TWI645899B_D0003.tif" /> Chemical Formula 3 In Chemical Formulas 1 to 3, M
<sup>a</sup>, M
<sup>b</sup>, M
<sup>c</sup> are each independently selected from the group consisting of copper, silver, gold, zinc, cadmium, and mercury, X
<sup>a</sup> is selected from the group consisting of 矽 and 锗, X
<sup>b</sup> and X
<sup>c</sup> are each independently selected from the group consisting of phosphorus and arsenic, M
<sup>d</sup>, M
<sup>e</sup> and M
<sup>f</sup> are each independently selected from the group consisting of molybdenum and tungsten, n represents a positive integer from 1 to 4, q represents a positive integer from 1 to 3, and p represents a positive integer from 1 to 6. .
</p><p>The effect of the present invention is that the method for producing ethylene from an ethanol raw material can effectively reduce the reaction temperature of the dehydration reaction of ethanol by using the supported heteropolyacid salt catalyst, thereby reducing energy consumption, and The process for producing ethylene from an ethanol feedstock provides higher ethanol conversion and higher ethylene selectivity. </p><p> Another effect of the present invention is that in the method for producing ethylene from an ethanol raw material, even if the supported heteropolyacid salt catalyst which has been used for catalyzing the dehydration reaction of ethanol is recovered and reused, The method for producing ethylene from an ethanol raw material can still carry out an ethanol dehydration reaction at a lower reaction temperature, and obtain a high ethanol conversion rate and an ethylene selectivity. </p></disclosure><mode-for-invention><p>The following is a detailed description of the present invention:</p> <p> The specific operation of the method for producing ethylene from an ethanol raw material comprises the following steps: The supported heteropolyacid salt catalyst is placed in a reactor; the ethanol feedstock is vaporized into ethanol gas; and the ethanol gas is introduced into the reactor by a carrier gas, and the carrier type is mixed The ethanol gas is subjected to a dehydration reaction of ethanol in the presence of an acid salt catalyst to obtain a gaseous product containing ethylene. The gas product formed by the dehydration reaction contains diethyl ether and water in addition to ethylene. More preferably, the method for producing ethylene from the ethanol raw material may further comprise the following steps: cooling the diethyl ether and water in the gaseous product. To separate ethylene. Among them, the manner in which the diethyl ether and water in the gaseous product are cooled is, for example but not limited to, the use of a gas-liquid separator. The obtained diethyl ether can be further recovered into the reactor and then subjected to a dehydration reaction to form ethylene, which can further increase the yield of ethylene. </p><p> wherein the ethanol raw material is generally referred to as a raw material containing ethanol, and the concentration thereof is not particularly limited, and the concentration of the ethanol raw material is, for example, 5 to 95% (v/v). </p><p> The carrier gas is, for example but not limited to, nitrogen, air. The humidity of the carrier gas is not particularly limited, and is, for example, but not limited to, 1 to 20%. </p><p>The reaction parameters in the dehydration reaction are not particularly limited, and the space velocity range is, for example but not limited to, 0.5 to 10 h.
<sup>-1</sup>, the pressure range is, for example but not limited to, 0.1 to 2 MPa.
</p><p> Preferably, the temperature of the dehydration reaction ranges from 180 to 450 ° C; more preferably, the temperature of the dehydration reaction ranges from 180 to 300 ° C; optimally, the temperature range of the dehydration reaction is 180 to 250 ° C. It should be particularly noted that in the method for producing ethylene from an ethanol raw material, the dehydration reaction can reach a relatively high ethanol conversion rate and a high ethylene selectivity at a temperature ranging from 180 to 250 ° C, but the ethanol raw material is produced. The temperature range of the dehydration reaction in the method of ethylene should not be limited to 180 to 250 ° C, but may be 180 to 300 ° C, or 180 to 450 ° C, and it is expected that when the temperature of the dehydration reaction is higher, the ethanol conversion The rate and ethylene selectivity will also increase relatively. </p><p> The supported heteropolyacid salt catalyst comprises the heteropolyacid salt compound and the carrier. </p><p> The heteropolyacid salt compound is selected from the group consisting of Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3.
<img he="21" wi="160" img-format="jpg" id="i0008" img-content="drawing" orientation="portrait" inline="no" file="TWI645899B_D0001.tif" /> Chemical formula 1
<img he="25" wi="160" img-format="jpg" id="i0008" img-content="drawing" orientation="portrait" inline="no" file="TWI645899B_D0002.tif" /> Chemical formula 2
<img he="25" wi="159" img-format="jpg" id="i0008" img-content="drawing" orientation="portrait" inline="no" file="TWI645899B_D0003.tif" /> Chemical Formula 3 In Chemical Formulas 1 to 3, M
<sup>a</sup>, M
<sup>b</sup>, M
<sup>c</sup> are each independently selected from the group consisting of copper, silver, gold, zinc, cadmium, and mercury, X
<sup>a</sup> is selected from the group consisting of 矽 and 锗, X
<sup>b</sup> and X
<sup>c</sup> are each independently selected from the group consisting of phosphorus and arsenic, M
<sup>d</sup>, M
<sup>e</sup> and M
<sup>f</sup> are each independently selected from the group consisting of molybdenum and tungsten, n represents a positive integer from 1 to 4, q represents a positive integer from 1 to 3, and p represents a positive integer from 1 to 6. .
</p><p> Preferably, in the chemical formulas 1 to 3, M
<sup>a</sup>, M
<sup>b</sup> and M
<sup>c</sup> are each independently selected from the group consisting of copper, silver, gold, and zinc. More preferably, in the chemical formulas 1 to 3, M
<sup>a</sup>, M
<sup>b</sup> and M
<sup>c</sup> are each independently selected from the group consisting of copper and silver.
</p><p> Preferably, in the chemical formula 1, X
<sup>a</sup> is selected from 矽, M
<sup>d</sup> is selected from tungsten.
</p><p>Preferably, in the chemical formulas 2 and 3, X
<sup>b</sup> and X
<sup>c</sup> are each independently selected from phosphorus, M
<sup>e</sup> and M
<sup>f</sup> are each independently selected from tungsten.
</p><p> Specific examples of the chemical formula 1 are, for example but not limited to, (AgH)
<sub>3</sub>)SiW
<sub>12</sub>O
<sub>40</sub>, (CuH
<sub>3</sub>)SiW
<sub>12</sub>O
<sub>40</sub> and so on.
</p><p> Specific examples of the chemical formula 2 are, for example but not limited to, (AgH)
<sub>2</sub>)P W
<sub>12</sub>O
<sub>40</sub>, (CuH
<sub>2</sub>)PW
<sub>12</sub>O
<sub>40</sub> and so on.
</p><p> Specific examples of the chemical formula 3 are, for example but not limited to, (AgH)
<sub>5</sub>)P
<sub>2</sub>W
<sub>18</sub>O
<sub>62</sub>, (CuH
<sub>5</sub>)P
<sub>2</sub>W
<sub>18</sub>O
<sub>62</sub> and so on.
Preferably, the carrier of the supported heteropolyacid salt catalyst is selected from the group consisting of silica, montmorillonite, unmodified clay (clay), bentonite ( Bentonite), celite, titanium dioxide, activated carbon, alumina, silica-alumina cogel, silica-titania cogel , a group consisting of silica-zirconia cogel, carbon coated alumina, zeolite, zinc oxide, and flame pyrolysed oxide group. </p><p> Preferably, in the chemical formulas 1 to 3, the total amount of the supported heteropolyacid salt catalyst is 100 wt%, and the M
<sup>a</sup>, M
<sup>b</sup> and M
The content ranges of <sup>c</sup> are each independently 0.5 wt% or more. More preferably, in Chemical Formulas 1 to 3, the total amount of the supported heteropolyacid salt catalyst is 100 wt%, and the M
<sup>a</sup>, M
<sup>b</sup> and M
The content ranges of <sup>c</sup> are each independently from 0.5 to 10% by weight. Most preferably, in the chemical formulas 1 to 3, the total amount of the supported heteropolyacid salt catalyst is 100 wt%, the M
<sup>a</sup>, M
<sup>b</sup> and M
The content ranges of <sup>c</sup> are each independently from 1 to 6 wt%.
</p><p> The preparation method of the supported heteropolyacid salt catalyst comprises the following steps: (1) providing a supported heteropolyacid catalyst, wherein the supported heteropolyacid catalyst contains a heteropoly acid and a carrier carrying the heteropolyacid; (2) providing a metal salt solution, wherein the metal species is selected from the group consisting of copper, silver, gold, zinc, cadmium and mercury; and (3). The supported heteropolyacid catalyst is reacted with the metal salt solution to obtain a crude product, and the supported heteropolyacid salt catalyst is obtained after drying the crude product. Preferably, the supported heteropolyacid catalyst is prepared, for example, but not limited to, incipient wetness impregnation, and the specific steps are detailed as follows: (1). The acid is dissolved in water to obtain a heteropoly acid solution; and (2) the heteropoly acid solution is mixed with a carrier to obtain a mixture, and the supported heteropolyacid catalyst is obtained by drying the mixture. Preferably, the heteropolyacid is selected from the group consisting of heteropolyacids having a Keggin structure and heteropolyacids having a Dawson structure. More preferably, the heteropoly acid is selected from the group consisting of Chemical Formula 4, Chemical Formula 5, and Chemical Formula 6,
<img he="21" wi="103" img-format="jpg" id="i0019" img-content="drawing" orientation="portrait" inline="no" file="TWI645899B_D0007.tif" /> Chemical formula 4
<img he="21" wi="103" img-format="jpg" id="i0019" img-content="drawing" orientation="portrait" inline="no" file="TWI645899B_D0008.tif" /> Chemical formula 5
<img he="21" wi="107" img-format="jpg" id="i0019" img-content="drawing" orientation="portrait" inline="no" file="TWI645899B_D0009.tif" /> Chemical Formula 6 In Chemical Formulas 4 to 6, X
<sup>a</sup> is selected from the group consisting of 矽 and 锗, X
<sup>b</sup> and X
<sup>c</sup> are each independently selected from the group consisting of phosphorus and arsenic, M
<sup>d</sup>, M
<sup>e</sup> and M
<sup>f</sup> are each independently selected from the group consisting of molybdenum and tungsten. Preferably, the heteropoly acid is selected from the group consisting of phosphotungstic acid, phosphomomlybdic acid, silicotungstic acid, and silicomolybdic acid. More preferably, the heteropolyacid is selected from the group consisting of phosphotungstic acid and tungstic acid.
</p><p> The concentration of the heteropolyacid solution is, for example but not limited to, 5 to 50% by weight. </p><p> The type of the carrier is as described above, and will not be described herein. </p><p> The weight ratio of the heteropolyacid solution to the carrier ranges, for example, but is not limited to, 0.5:1 to 1:5. </p><p> A method of drying the mixture of the heteropolyacid solution and the carrier, such as but not limited to, heating the mixture at a temperature ranging from 80 to 150 °C. </p><p> The metal salt solution is prepared by dissolving a metal salt in water. Specific examples of the metal salt are copper nitrate, silver nitrate, chloroauric acid salt, zinc nitrate, cadmium nitrate, mercury nitrate, and the like. The concentration of the metal salt solution ranges from 1 to 50% by weight. </p><p> The weight ratio of the supported heteropolyacid catalyst to the metal salt solution is, for example but not limited to, 100:0.5 to 100:10. </p><p> The supported heteropolyacid catalyst and the crude product formed by the reaction of the metal salt solution are dried, for example, but not limited to, at a temperature ranging from 80 to 150 °C. The invention is further described in the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting. </p><p>[Examples]</p><p> First, a supported ruthenium tungstate catalyst and a supported phosphotungstic acid catalyst used in the following examples will be described:</p><p>1 The preparation method of the supported ruthenium tungstate catalyst is to dissolve 6 g of tungstic acid in 12 ml of water to obtain a tungstic acid solution. 18 g of this thallium tungstic acid solution was mixed with 6 g of cerium oxide (manufacturer model: UniRegion Bio-Tech), and dried at 130 ° C to obtain the supported yttrium tungstic acid catalyst. </p><p>2. Preparation method of supported phosphotungstic acid catalyst: 6 g of phosphotungstic acid is dissolved in 12 ml of water to obtain a phosphotungstic acid solution. 18 g of this phosphotungstic acid solution was mixed with 6 g of cerium oxide (manufacturer model: UniRegion Bio-Tech), and after drying, the supported phosphotungstic acid catalyst was obtained. </p><p>[Example 1]</p><p> 0.189 g of silver nitrate was dissolved in 3 ml of distilled water to obtain a silver nitrate solution. The silver nitrate solution was slowly dropped into a supported ruthenium tungstate catalyst having a total weight of 12 g and stirred uniformly to obtain a crude product. The crude product was dried in an oven at 130 ° C to obtain a supported silver strontium tungstate catalyst [AgH barium tungstate compound (AgH)
<sub>3</sub>)SiW
<sub>12</sub>O
<sub>40</sub>, the content of silver is 1 wt%]. 3 ml of this supported strontium tungstate silver salt catalyst was placed in a fixed bed reactor. Using a liquid control pump, 95% (v/v) ethanol is pumped into a preheating tank to vaporize into ethanol gas, and nitrogen gas is used as a carrier gas (humidity 5%) to carry the ethanol gas. Into the fixed bed reactor at a space velocity of 1 h
The gas product of Example 1 was obtained by subjecting <sup>-1</sup>, a reaction temperature of 220 ° C, and a reaction pressure of 0.1 MPa to carry out dehydration of ethanol.
</p><p>[Example 2]</p><p> 0.992 g of silver nitrate was dissolved in 3 ml of distilled water to obtain a silver nitrate solution. The silver nitrate solution was slowly dropped into a supported ruthenium tungstate catalyst having a total weight of 12 g and stirred uniformly to obtain a crude product. The crude product was dried in an oven at 130 ° C to obtain a supported silver strontium tungstate catalyst [AgH barium tungstate compound (AgH)
<sub>3</sub>)SiW
<sub>12</sub>O
<sub>40</sub>, the content of silver is 5 wt%]. 3 ml of this supported strontium tungstate silver salt catalyst was placed in a fixed bed reactor. Using a liquid quality control pump, 95% (v/v) ethanol is pumped into a preheating tank to vaporize into ethanol gas, and nitrogen gas is used as a carrier gas (humidity 5%) to bring the ethanol gas into the fixed bed. In the reactor, at a space velocity of 1 h
The gas product of Example 2 was obtained by conducting a dehydration reaction of ethanol under the conditions of <sup>-1</sup>, a reaction temperature of 200 ° C, and a reaction pressure of 0.1 MPa.
</p><p>[Example 3]</p><p> Example 3 was carried out in the same manner as in Example 2, except that the dehydration reaction of ethanol was carried out at a reaction temperature of 220 ° C. The gaseous product of Example 3 was obtained. </p><p>[Example 4]</p><p> Example 4 was carried out in the same manner as in Example 2, except that the dehydration reaction of ethanol was carried out at a reaction temperature of 250 ° C. The gaseous product of Example 4 was obtained. </p><p>[Example 5]</p><p> 0.901 g of copper nitrate was dissolved in 3 ml of distilled water to obtain a copper nitrate solution. The copper nitrate solution was slowly dropped into a supported ruthenium tungstate catalyst having a total weight of 12 g and stirred uniformly to obtain a crude product. The crude product was dried in an oven at 130 ° C to obtain a supported copper strontium tungstate catalyst [CuH bismuth tungstate compound (CuH)
<sub>3</sub>)SiW
<sub>12</sub>O
<sub>40</sub>, the content of copper is 2.5 wt%]. 3 ml of this supported copper barium tungstate catalyst was placed in a fixed bed reactor. Using a liquid quality control pump, 95% (v/v) ethanol is pumped into a preheating tank to vaporize into ethanol gas, and nitrogen gas is used as a carrier gas (humidity 5%) to bring the ethanol gas into the fixed bed. In the reactor, at a space velocity of 1 h
The gas product of Example 5 was obtained by conducting a dehydration reaction of ethanol under the conditions of <sup>-1</sup>, a reaction temperature of 220 ° C, and a reaction pressure of 0.1 MPa.
</p><p>[Example 6]</p><p> 0.992 g of silver nitrate was dissolved in 3 ml of distilled water to obtain a silver nitrate solution. The silver nitrate solution was slowly dropped into a supported phosphotungstic acid catalyst having a total weight of 12 g and stirred uniformly to obtain a crude product. The crude product was dried in an oven at 130 ° C to obtain a supported phosphotungstic acid silver salt catalyst [phosphorus tungstate silver salt compound (AgH)
<sub>2</sub>)PW
<sub>12</sub>O
<sub>40</sub>, the content of silver is 5 wt%]. 3 ml of this supported phosphotungstate silver salt catalyst was placed in a fixed bed reactor. Using a liquid quality control pump, 95% (v/v) ethanol is pumped into a preheating tank to vaporize into ethanol gas, and nitrogen gas is used as a carrier gas (humidity 5%) to bring the ethanol gas into the fixed bed. In the reactor, at a space velocity of 1 h
The gas product of Example 6 was obtained by conducting a dehydration reaction of ethanol under the conditions of <sup>-1</sup>, a reaction temperature of 220 ° C, and a reaction pressure of 0.1 MPa.
</p><p>[Example 7]</p><p> Example 7 was carried out in the same manner as in Example 3, except that the carrier-type silver tungstate silver salt catalyst was repeatedly used for dehydration of five times of ethanol. reaction. </p><p>[Comparative Example]</p><p>[Comparative Example 1]</p><p>6 g of tungstic acid was dissolved in 12 ml of distilled water to obtain a tungstic acid. Solution. The ruthenium tungstate solution was slowly dropped into 6 g of cerium oxide and stirred to obtain a crude product. After the crude product was dried in an oven at 130 ° C, a heterogeneous catalyst was obtained. 3 ml of this heterogeneous catalyst was placed in a fixed bed reactor. Using a liquid quality control pump, 95% (v/v) ethanol is pumped into a preheating tank to vaporize into ethanol gas, and nitrogen gas is used as a carrier gas (humidity 5%) to bring the ethanol gas into the fixed bed. In the reactor, at a space velocity of 1 h
The gas product of Comparative Example 1 was obtained by dehydration of ethanol under the conditions of <sup>-1</sup>, a reaction temperature of 220 ° C, and a reaction pressure of 0.1 MPa.
</p><p>[Comparative Example 2]</p><p> Comparative Example 2 was carried out in the same manner as in Comparative Example 1, except that the dehydration reaction of ethanol was carried out at a reaction temperature of 250 ° C. The gas product of Comparative Example 2 was obtained. </p><p>[Comparative Example 3]</p><p> 6 g of phosphotungstic acid was dissolved in 12 ml of distilled water to obtain a phosphotungstic acid solution. The phosphotungstic acid solution was slowly dropped into 6 g of cerium oxide and stirred to obtain a crude product. After the crude product was dried in an oven at 130 ° C, a heterogeneous catalyst was obtained. 3 ml of this heterogeneous catalyst was placed in a fixed bed reactor. Using a liquid quality control pump, 95% (v/v) ethanol is pumped into a preheating tank to vaporize into ethanol gas, and nitrogen gas is used as a carrier gas (humidity 5%) to bring the ethanol gas into the fixed bed. In the reactor, at a space velocity of 1 h
The gas product of Comparative Example 3 was obtained by conducting a dehydration reaction of ethanol under the conditions of <sup>-1</sup>, a reaction temperature of 220 ° C, and a reaction pressure of 0.1 MPa.
</p><p>[Property Evaluation]</p><p>The gas products of each of the examples and the comparative examples were analyzed using a gas chromatograph (manufacturer model: Bruker 450-GC) to measure ethanol conversion. Rate, ethylene selectivity and ether selectivity. The results are shown in Tables 1 to 3. </p><p><p>Table 1
<tables><table><TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td></td><td> Heteropolyacid salt catalyst </td><td> Reaction temperature (°C) </td><td> Ethanol conversion rate (%) </td><td> Ethylene selectivity (%) </td><td> Ether selection rate (%) </td></tr><tr><td> Example </td><td> 1 </td><td> Silver strontium tungstate (silver content 1 wt%) </td><td> 220 </td><td> 99.5 </td><td> 85.2 </td><;td> 11.6 </td></tr><tr><td> 2 </td><td> silver tungstate silver (silver content 5 wt%) </td><td> ; 200 </td><td> 99.4 </td><td> 94.1 </td><td> 2.4 </td></tr><tr><td> 3 </td><td> silver tungstate silver (silver content 5 wt%) </td><td> 220 </td><td> 99.8 </td><td> 99.5 </td><td> <0.5 </td></tr><tr><td> 4 </td><td> Silver tungstate silver (silver content 5 wt%) </td><td> 250 </td><td> 99.9 </td><;td> 99.6 </td><td> <0.5 </td></tr><tr><td> 5 </td><td> bismuth tungstate (copper content) 2.5wt%) </td><td> 220 </td><td> 96.1 </td><td> 86.5 </td><td> 10.7 </td><;/tr><tr><td> 6 </td><td> Silver phosphotungstate (silver content 5 wt%) </td><td> 220 </td><td> 98.3 </td><td> 96.8 </td><td> 1.9 </td></tr></TBODY></TABLE></table></tables> </p><p>Table 2
<tables><table><TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td></td><td> Type heteropolyacid salt catalyst </td><td> reaction temperature (°C) </td><td> times </td><td> ethanol conversion rate (%) </td><td> Ethylene selectivity (%) </td></tr><tr><td> Example </td><td> 7 </td><td> Silver tungstate (silver content 5 wt%) </td><td> 220 </td><td> 1st </td><td> 99.8 </td><td> 99.5 </td></tr><tr><td>2nd</td><td> 99.8 </td><td> 99.2 </td></ Tr><tr><td>3rd</td><td> 99.7 </td><td> 99.3 </td></tr><tr><td> ; 4th </td><td> 99.9 </td><td> 99.6 </td></tr><tr><td>5th</td><td> 99.8 </td><td> 99.5 </td></tr></TB ODY></TABLE></table></tables></p><p>Table 3
<tables><table><TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td></td><td> Phase catalyst </td><td> Reaction temperature (°C) </td><td> Ethanol conversion rate (%) </td><td> Ethylene selectivity (%) </td> ;<td> Ether selection rate (%) </td></tr><tr><td> Comparative example </td><td> 1 </td><td> Tungstic acid </td><td> 220 </td><td> 94.3 </td><td> 79.5 </td><td> 0.3 </td></tr><tr><td> 2 </td><td> Tungstic acid </td><td> 250 </td><td> 94.2 </td><lt ;td> 83.7 </td><td> 5.6 </td></tr><tr><td> 3 </td><td> phosphotungstic acid </td><td> 220 </td><td> 98.0 </td><td> 91.2 </td><td> <0.5 </td></tr></TBODY> ;</TABLE></table></tables></p><p> As can be seen from the results of Table 1, implementation 1-6 Through the use of the carrier heteropolyacid salt catalyst and the reaction temperature of 200 to 250 deg.] C dehydration reaction of ethanol, the ethanol conversion rate reached 96.1 to 99.9%, the ethylene selectivity of 85.2 to 99.6%. It is demonstrated that Examples 1 to 6 can effect the ethanol dehydration reaction at a low reaction temperature by using the supported heteropolyacid salt catalyst, and obtain a higher ethanol conversion rate and a higher ethylene selectivity. The selectivity of diethyl ether in Examples 1 to 6 was less than 0.5 to 11.6, and the obtained diethyl ether was recovered into a process for further dehydration reaction to obtain ethylene, which contributed to an increase in the overall yield of ethylene. </p><p> It is worth mentioning that, from the data of Example 7 in Table 2, even if the supported phosphotungstate silver salt catalyst is repeatedly used five times for the ethanol dehydration reaction, the reaction temperature at 220 ° C The ethanol conversion rate is still maintained at 99.7 to 99.9%, and the ethylene selectivity is between 99.2 and 99.6%. It can be seen that the method for producing ethylene from an ethanol raw material can be repeatedly used by using a supported heteropolyacid salt catalyst, and the ethanol dehydration reaction can still obtain higher ethanol conversion at a low reaction temperature. Rate and ethylene selectivity. </p><p> From the results of Table 3, it is known that Comparative Examples 1 to 2 use a heterogeneous catalyst and carry out a dehydration reaction of ethanol at a reaction temperature of 220 to 250 ° C, and the conversion of ethanol is only 94.2 to 94.3%. The rate is only 79.5 to 83.7%. From this, it can be seen that Comparative Examples 1 to 2 have poor ethanol conversion and ethylene selectivity when ethanol dehydration reaction is carried out at a low reaction temperature, and in order to obtain a higher ethanol conversion rate and ethylene selectivity, it is necessary to further increase ethanol dehydration. The reaction temperature at the time of the reaction. </p><p> At a reaction temperature of 220 ° C, the ethylene selectivity obtained by the ethanol dehydration reaction using the supported silver phosphotungstate catalyst of Example 6 was 96.8%, and Comparative Example 3 was carried out using a heterogeneous catalyst. The ethylene selectivity obtained by the ethanol dehydration reaction is low, only 91.2%. From this, it is understood that in Comparative Example 3, in order to obtain a high ethylene selectivity, it is necessary to further increase the reaction temperature in the ethanol dehydration reaction. </ RTI> <p> In summary, the method for producing ethylene from an ethanol raw material of the present invention can effectively reduce the reaction temperature of the dehydration reaction of ethanol by using the supported heteropolyacid salt catalyst, thereby reducing energy consumption, and The method for producing ethylene from an ethanol raw material is subjected to an ethanol dehydration reaction at a low reaction temperature to obtain a high ethanol conversion rate and a high ethylene selectivity. And in the method for producing ethylene from an ethanol raw material, even if the supported heteropolyacid salt catalyst which has been used for catalyzing the dehydration reaction of ethanol is recovered and reused, the method for producing ethylene from the ethanol raw material can still be at a lower reaction temperature. The ethanol dehydration reaction is carried out, and a high ethanol conversion rate and an ethylene selectivity are obtained, so that the object of the present invention can be achieved. The above is only the embodiment of the present invention, and the scope of the invention is not limited thereto, and the simple equivalent of the patent application scope and the patent specification content of the present invention is provided. Variations and modifications are still within the scope of the invention. </p></mode-for-invention><description-of-drawings><description-of-element /></description-of-drawings><bio-deposit /><sequence-list-text />